The chemistry of 3,3-dimethyl-1,2-diazabicyclo(2.2.2)octane, as well as 3-methyl and unmethylated analogues is being investigated. The dimethyl system is conformationally restricted to have a low N1,N2 electronic interaction, which is predicted to allow preparation of derivatives with leaving groups attached to N2; hydrazines with leaving groups attached to nitrogen remain unknown because they ionize and usually undergo rapid subsequent reactions. The conformationally restricted compounds should allow alkylated derivatives of triazene, tetrazane, and 3-hexazene to be obtained. Study of electronic interactions in these compounds, as well as thermodynamic and kinetic studies on their radical ions are in progress. The thermodynamics for stabilization of amino nitrogen radical cations for a variety of substituents is possible because of the long lifetimes for radical cations in the 9-azabicyclo(3.3.1)nonyl system, and such studies are being extended to sulfur and selenium-containing radical cations. The influence of molecular conformation on intramolecular interactions in diamagnetic species and radical ions is being studied using a wide range of experimental techniques including cyclic voltammetry, PE spectroscopy, VT-13C and 1H-NMR, and ESR. Our goal is understanding how the kinetics and thermodynamics of electron transfer reactions is controlled in biological systems.